Fungicidal composition

ABSTRACT

A fungicidal composition of 
     a) methyl α-methoximino-2-[(2-methylphenoxy)-methyl]-phenylacetate ##STR1## and b) 4-(2-methyl-3-[4-tert-butylphenyl]-propyl)-2,6-dimethylmorpholine (fenpropimorph) ##STR2## or the active ingredient tridemorph or the active ingredient fenpropidin, and methods of combating fungi with this composition.

This is a division of application Ser. No. 08/025,577, filed on Mar. 3,1993, now U.S. Pat. No. 5,286,724, which is a division of applicationSer. No. 07/904,654, filed on Jun. 26, 1992, now U.S. Pat. No.5,242,920.

The present invention relates to fungicidal compositions having asynergistic fungicidal action, and to methods of combating fungi withthese compositions.

It is known to use methylα-methoximino-2-[(2-methylphenoxy)-methyl]phenylacetate ##STR3## as afungicide (EP 253,213). It is also known to use the active ingredient4-(2-methyl-3-[4-tert-butylphenyl]-propyl)-2,6-dimethylmorpholine##STR4## and the active ingredients tridemorph and fenpropidin and theirsalts as fungicides (DE 26 56 747).

We have now found that a composition of

a) methyl α-methoximino-2-[(2-methylphenoxy)-methyl]-phenylacetate##STR5## and b)4-(2-methyl-3-[4-tert-butylphenyl]-propyl)-2,6-dimethylmorpholine(fenpropimorph) ##STR6## or the active ingredient tridemorph or theactive ingredient fenpropidin has a synergistic fungicidal action. Themixture ratio (by weight) of compounds a) and b) is such that asynergistic fungicidal action occurs, for example a ratio of a):b) offrom 5:1 to 1:5, especially from 3:1 to 1:3, and preferably from 2:1 to1:2. The synergistic effect of the composition is apparent from the factthat the fungicidal action of the composition of a)+b) is greater thanthe sum of the fungicidal actions of a) and b).

Component a) may be present in two stereoisomer forms because of the--C═N double bond. The (E) isomer is preferred.

The invention embraces compositions containing pure isomers of compounda), especially the (E) isomer, and compositions containing mixtures ofisomers.

The component fenpropimorph may be present in two stereoisomer forms(morpholine ring), the cis isomer being preferred.

The invention embraces compositions containing pure isomers of thecompound fenpropimorph, especially the cis isomer, and compositionscontaining mixtures of isomers.

Preferred compositions are those which contain component a)predominantly in the form of the (El isomer, and component b)predominantly as the cis isomer: ##STR7##

The active ingredient fenpropimorph b) may also be present in the formof its salts. These compositions too are embraced by the invention.

Salts are produced by reaction with acids, e.g., hydrohalic acids suchas hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodicacid, or sulfuric acid, phosphoric acid, nitric acid or organic acidssuch as acetic acid, trifluoroacetic acid, trichloroacetic acid,propionic acid, glycolic acid, lactic acid, succinic acid, citric acid,benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonicacid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid,p-aminosalicylic acid and 1,2-naphthalenedisulfonic acid.

Usually, the pure active ingredients a) and b) are advantageously used,to which other active ingredients such as insecticides, acaricides,nematicides, herbicides, other fungicides, growth regulators and/orfertilizers may be added.

The fungicidal compositions according to the invention may be appliedfor instance in the form of directly sprayable solutions, powders,suspensions (including high-percentage aqueous, oily or othersuspensions), dispersions, emulsions, oil dispersions, pastes, dusts,broadcasting agents, or granules by spraying, atomizing, dusting,broadcasting or watering. The forms of application depend entirely onthe purpose for which the agents are being used, but they must ensure asfine a distribution of the composition according to the invention aspossible.

Normally, the plants are sprayed or dusted with the compositions, or theseeds of the plants are treated with the compositions.

The formulations are prepared in known manner, e.g., by extending thecomposition with solvents and/or carriers, if desired using emulsifiersand dispersants; if water is employed as diluent, other organic solventsmay also be used as auxiliary solvents. Examples of suitable auxiliariesare essentially solvents such as aromatics (e.g., xylene), chlorinatedaromatics (e.g., chlorobenzenes), paraffins (e.g., petroleum fractions),alcohols (e.g., methanol, butanol), ketones (e.g., cyclohexanone),amines (e.g., ethanolamine, dimethylformamide), and water; carriers suchas natural rock flours (e.g., kaolins, clays, talc and chalk), andsynthetic rock flours (e.g., highly disperse silicic acid, silicates);emulsifiers such as nonionic and anionic emulsifiers (e.g.,polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates), and dispersants such as lignin-sulfite waste liquors andmethylcellulose.

Examples of surfactants are: alkali metal, alkaline earth metal andammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid,phenolsulfonic acid, naphthalenesulfonic acid anddibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, andsalts of sulfated hexadecanols, heptadecanols, and octadecanols, saltsof fatty alcohol glycol ethers, condensation products of sulfonatednaphthalene and naphthalene derivatives with formaldehyde, condensationproducts of naphthalene or naphthalenesulfonic acids with phenol andformaldehyde, polyoxyethylene octylphenol ethers, ethoxylatedisooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcoholethylene oxide condensates, ethoxylated castor oil, polyoxyethylenealkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycolether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose.

Powders, dusts and broadcasting agents may be prepared by mixing orgrinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may beprepared by bonding the active ingredients to solid carriers. Examplesof solid carriers are mineral earths such as silicic acids, silica gels,silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole,loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesiumsulfate, magnesium oxide, ground plastics, fertilizers such as ammoniumsulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetableproducts such as grain meals, bark meal, wood meal, and nutshell meal,cellulosic powders, etc.

The compositions are extremely effective on a broad spectrum ofphytopathogenic fungi, in particular those from the class consisting ofthe Ascomycetes and Basidiomycetes. Some of them have a systemic actionand can be used as foliar and soil fungicides.

The compositions are of particular interest for controlling a largenumber of fungi in various crops or their seeds, especially wheat, rye,barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugarcane, grapes and other fruit, and ornamentals, and in vegetables such ascucumbers, beans and cucurbits, and the seeds of these plants.

The compositions are applied by treating the fungi, or the seed, plantsor materials to be protected against fungus attack, or the soil with afungicidally effective amount of them.

The compositions may be applied before or after infection of thematerials, plants or seed by the fungi.

The compositions are particularly useful for controlling the followingplant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia solani in cotton,

Ustilago species in cereals and sugar cane,

Venturia inaequalis (scab) in apples,

Helminthosporium species in cereals,

Septoria nodorum in wheat,

Rhynchosporium in cereals,

Botrytis cinerea (gray mold) in strawberries and grapes,

Cercospora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fusarium and verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in fruit and vegetables.

The novel compositions may also be used for protecting materials(timber), e.g., against Paecilomyces variotii.

The fungicidal agents generally contain from 0.1 to 95, and preferablyfrom 0.5 to 90, wt % of active ingredient.

The application rates of the compositions according to the inventiondepend on the effect desired, and range from 0.01 to 3 Kg of activeingredient composition per hectare.

When the compositions are used for treating seed, application rates offrom 0.001 to 50, and preferably from 0.01 to 10, g per Kg of seed aregenerally required.

EXAMPLE 1

Eradicative action on wheat mildew

Wheat plants of the "Kanzler" variety were treated, after they haddeveloped 3 leaves, in one experiment with wheat mildew (Erysiphegraminis vat. tritici) which was unsusceptible to fungicides containinga triazole radical in the molecule, and in a further experiment withwheat mildew which was susceptible to fungicides containing a triazoleradical in the molecule, and were treated, after fungus attack haddeveloped on 5% of the leaf surface, with the stated concentrations ofaqueous formulations of the active ingredients. The amount of watercorresponded to 400 liters/ha. The plants were cultivated in thegreenhouse for 20 days at 18° to 22° C. The leaf area under fungusattack was then assessed in percent. These figures were then convertedinto degrees of action. The degree of action in the untreated controlwas set at 0. The degree of action when 0% of the leaf area was attackedby fungus was set at 100. The expected degrees of action of the activeingredient composition were determined in accordance with the Colbyformula (Colby, S. R., "Calculating synergistic and antagonisticresponses of herbicide combinations", Weeds, 15, pp. 20-22, 1967) andcompared with the degrees of action observed.

The values for the fungicidal action varied between the individualexperiments because the plants in the individual experiments exhibitedvarying degrees of attack; for this reason, only the results within thesame experiment can be compared with each other. ##EQU1## E=expecteddegree of action, expressed in % of the untreated control, when activeingredients A and B are used in concentrations of m and n

x=degree of action, expressed in % of the untreated control, when activeingredient A is used in a concentration of m

y=degree of action, expressed in % of the untreated control, when activeingredient B is used in a concentration of n ##STR8##

Experiment 1:

Eradicative action on Erysiphe graminis in wheat (Erysiphe graministriazole-resistant)

    ______________________________________                                                     Active ingredient                                                                           Degree of action                                                conc. in spray                                                                              in % of untreated                                  Active ingredient                                                                          liquor in %   control                                            ______________________________________                                        Control (untreated)                                                                        --             0                                                 I.               0.05          40                                             II.  Fenpropimorph                                                                             0.05          20                                             III. Fenpropidin 0.05          23                                             IV.  Tridemorph  0.05          13                                             Composition acc. to invention                                                 I. + II.                                                                             Ratio 1:3 0.01 + 0.03                                                                             83                                                 I. + III.                                                                            Ratio 1:3 0.01 + 0.03                                                                             89                                                 I. + IV.                                                                             Ratio 1:3 0.01 + 0.03                                                                             67                                                 ______________________________________                                    

The results show that 0.04% (0.01+0.03) of the composition has a betterfungicidal action than 0.05% of the individual active ingredients.

The same experiment with triazole-susceptible Erysiphe graminisconfirmed the above results.

Experiment 2:

Eradicative action on Erysiphe graminis in wheat (Erysiphe graministriazole-resistant)

    ______________________________________                                                      Active ingredient                                                                          Degree of action                                                 conc. in spray                                                                             in % of untreated                                  Active ingredient                                                                           liquor in %  control                                            ______________________________________                                        Control (untreated)                                                                          --           0                                                 I.  Active ingredient                                                                           0.1          65                                                               0.001        21                                             II. Fenpropimorph 0.1          52                                                               0.01         11                                             ______________________________________                                        Composition acc. to                                                                        Degree of action                                                                            Degree of action                                   invention    observed      calculated*.sup.)                                  ______________________________________                                        I + II                                                                              0.01 + 0.01                                                                              55            29.7                                                 Ratio 1:1                                                               I + II                                                                              0.1 + 0.1  100           83.2                                                 Ratio 1:1                                                               I + II                                                                              0.1 + 0.01 87            68.8                                                 Ratio 10:1                                                              I + II                                                                              0.01 + 0.1 79            62.1                                                 Ratio 1:10                                                              ______________________________________                                         *.sup.) Calculated by the Colby formula                                  

The same experiment with triazole-susceptible Erysiphe graminisconfirmed the above results.

What we claim is:
 1. A fungicidal composition comprising asynergistically fungicidally effective amount of a composition ofa:methyl α-methoximino-2-[(2-methylphenoxy)-methyl]-phenylacetate of theformula ##STR9## and b:N-[3-(4-tert.-butylphenyl)-2-methylpropyl]-piperidine ##STR10## in aratio of a:b from 5:1 to 1:5.
 2. A method for combating fungi,comprising the step of applying a synergistically fungicidally effectiveamount of a composition of claim 1 to the fungi or to seeds, plants ormaterials subject to fungal attack.
 3. A fungicidal composition of claim1, wherein the weight ratio of a:b is from 3:1 to 1:3.
 4. A fungicidalmethod according to claim 2, wherein the weight ratio of a:b is from 3:1to 1:3.
 5. A fungicidal composition of claim 1, wherein the weight ratioof a:b is from 1:2 to 2:1.
 6. A fungicidal method according to claim 2,wherein the weight ratio of a:b is from 1:2 to 2:1.
 7. A fungicidalagent containing a synergistically fungicidally effective amount of acomposition ofa) methylα-methoximino-2-[(2-methylphenoxy)-methyl]phenylacetate ##STR11## and b)N-[3-(4-tert.-butylphenyl)-2-methylpropyl]-piperidine ##STR12## in aratio of a:b of about 1:3.
 8. A process for combating fungi, comprisingcontacting fungi or the materials, areas, plants, or seeds threatened byfungus attack with a synergistically fungicidally effective amount of acomposition ofa) methylα-methoximino-2-[(2-methylphenoxy)-methyl]phenylacetate ##STR13## and b)N-[3-(4-tert.-butylphenyl)-2-methylpropyl]-piperidine ##STR14## in aratio of a:b of about 1:3.